KR101995076B1 - Colored curable resin composition - Google Patents

Abstract

[식 (1)에서, R¹ 및 R²는 각각 독립적으로 치환기를 갖고 있더라도 좋은 페닐기를 나타낸다. R³ 및 R⁴는 각각 독립적으로 탄소수 1∼10의 1가의 포화 탄화수소기를 나타낸다. R⁵는 -OH, -SO₃H 등을 나타낸다.
R⁶ 및 R⁷은 각각 독립적으로 수소 원자 또는 탄소수 1∼6의 알킬기를 나타낸다. m은 0∼4의 정수를 나타낸다.]The present invention relates to a colorant comprising a colorant, a resin, a polymerizable compound, a polymerization initiator and an organometallic compound, wherein the colorant is a colorant containing a compound represented by the formula (1), and the molar extinction coefficient Is smaller than the maximum molar extinction coefficient in the visible light region of the compound represented by the formula (1).

[In the formula (1), R ¹ and R ² each independently represent a phenyl group which may have a substituent. R ³ and R ⁴ each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. R ⁵ represents -OH, -SO ₃ H, or the like.
R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; and m represents an integer of 0 to 4.]

Description

COLORED CURABLE RESIN COMPOSITION [0002]

The present invention relates to a colored curable resin composition.

The colored curable resin composition is used in the production of color filters used in display devices such as liquid crystal display panels, electroluminescence panels and plasma display panels. Examples of such a color-curable resin composition include dyes obtained by sulfonating a compound represented by the formula (A2-1a) and a compound represented by the formula (A2-1b) with 2-ethylhexylamine as colorants; (JP2011-118365-A), which further contains zinc bis (dibutyldithiocarbamate) and pigment blue.

The conventionally known coloring curable resin composition does not necessarily satisfy the brightness of the color filter obtained by the coloring curable resin composition.

The present invention includes the following inventions.

[1] A colored curable resin composition comprising a colorant, a resin, a polymerizable compound, a polymerization initiator, and an organometallic compound,

Wherein the colorant comprises a compound represented by the formula (1)

The maximum value of the molar extinction coefficient in the visible light region of the organometallic compound is smaller than the maximum value of the molar extinction coefficient in the visible light region of the compound represented by the formula (1).

[In the formula (1), R ¹ and R ² independently represent a phenyl group which may have a substituent.

R ³ and R ⁴ independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom, and the aromatic hydrocarbon group The hydrogen atom contained may be substituted with an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and -CH ₂ - included in the saturated hydrocarbon group is substituted with -O-, -CO- or -NR ¹¹ - It may be.

R ¹ and R ³ may form a ring containing a nitrogen atom together with the nitrogen atom, and R ² and R ⁴ may form a ring together with the nitrogen atom.

R ⁵ is _{-OH, -SO 3 H, -SO 3} - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8 -, -SO 3 R 8 or -SO ₂ NR ⁹ R ¹⁰ .

R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;

m represents an integer of 0 to 4; When m is 2 or more, plural R ^{5 s} may be the same or different.

R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.

Z ⁺ represents ⁺ N (R < ¹¹ >) ₄ , Na ⁺ or K ⁺ .

R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and R ⁹ and R ¹⁰ may be bonded to each other to form a 3- to 10-membered nitrogen-containing heterocycle together with the nitrogen atom .

R ¹¹ each independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.

[2] The color-curable resin composition according to [1], wherein the organometallic compound is at least one selected from the group consisting of a compound represented by the formula (F1), a compound represented by the formula (F2), and a hydrate thereof.

Wherein W ¹ and W ² each independently represent a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms and the aliphatic hydrocarbon group and the aromatic hydrocarbon group included in the aromatic hydrocarbon group The hydrogen atom may be substituted with a hydroxy group.

M ¹ represents a metal atom.

x represents an integer of 1 to 3, and when x is 2 or more, a plurality of W ¹ and W ² may be the same or different.

[In the formula (F2), W ³ and W ⁴ each independently represent a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, and the hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with a halogen atom.

M ² represents a metal atom.

y represents an integer of 1 to ^3, and when y is 2 or more, a plurality of W ³ and W ⁴ may be the same or different.

[3] The colored curable resin composition according to [1] or [2], wherein the colorant further comprises a pigment.

[4] A color filter formed by the colored curable resin composition according to any one of [1] to [3].

[5] A display device comprising the color filter according to [4].

According to the colored curable resin composition of the present invention, a high-definition color filter can be formed.

1 is a schematic view for explaining a method of manufacturing a color filter of the present invention.
2 is a schematic view for explaining a method of manufacturing a color filter of the present invention.
3 is a schematic view for explaining a method of manufacturing a color filter of the present invention.

The colored curable resin composition of the present invention comprises a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D) and an organometallic compound (M).

The colorant (A) preferably contains the compound represented by the above formula (1) (hereinafter sometimes referred to as " compound (1) ") and further contains the pigment (A1).

The colored curable resin composition of the present invention preferably further comprises a solvent (E).

The colored curable resin composition of the present invention may further contain a dye (A2) different from the compound (1), a polymerization initiator (D1) and a surfactant (F) And at least one kind selected from the group consisting of

On the other hand, in the present specification, the compounds exemplified as respective components can be used singly or in combination of a plurality of species, unless specifically appreciated.

≪ Compound (1) >

The color-curable resin composition of the present invention contains the compound (1) as a colorant, whereby a high-definition color filter can be produced. The compound (1) may be a tautomer thereof.

[In the formula (1), R ¹ to R ⁷ and m each have the same meaning as described above.]

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, , A straight chain alkyl group having 1 to 20 carbon atoms such as a decyl group, a dodecyl group, a hexadecyl group and an icosyl group; Branched chain alkyl groups having 3 to 20 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl and 2-ethylhexyl; An alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and tricyclodecyl group.

Examples of-OR ⁸ include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy and icosyloxy.

Examples of -CO ₂ R ⁸ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, and an icosyloxycarbonyl group.

Examples of -SR ⁸ include a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group, and an icosylsulfanyl group.

Examples of -SO ₂ R ⁸ include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and an icosylsulfonyl group.

Examples of -SO ₃ R ⁸ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.

Examples of -SO ₂ NR ⁹ R ^10, for example a sulfamoyl group;

N-isopropylsulfamoyl group, N-methylsulfamoyl group, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, (1, 1-dimethylpropyl) sulfamoyl group, N- (1, 2-dimethylpropyl) sulfamoyl group, N-methylpyrrolyl group, N- (2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (3-methylbutyl) sulfamoyl group, an N-cyclopentylsulfamoyl group, an N-hexylsulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) An N-1-substituted sulfamoyl group such as a sulfamoyl group, N- (1,5-dimethyl) hexylsulfamoyl group and N- (1,1,2,2-tetramethylbutyl) sulfamoyl group;

N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-diethylamino groups such as N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N-2-substituted sulfamoyl group, and the like.

R ⁹ and R ¹⁰ may be bonded to each other to form a 3- to 10-membered nitrogen-containing heterocyclic ring together with the nitrogen atom. That is, the atom constituting the monovalent saturated hydrocarbon group in R ⁹ and the monovalent saturated hydrocarbon group in R ¹⁰ may be bonded to form a 3- to 10-membered nitrogen-containing heterocyclic ring together with the nitrogen atom. Examples of the heterocyclic ring include the following.

As the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in R ³ and R ⁴ , saturated hydrocarbon groups represented by R ⁸ include those having 1 to 10 carbon atoms in the exemplified group.

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include a phenyl group and a naphthyl group. Of these groups in which hydrogen atoms contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms may be substituted, examples of the alkyl group having 1 to 3 carbon atoms include methyl group, ethyl group, n-propyl group and isopropyl group, and alkoxy groups having 1 to 3 carbon atoms Include a methoxy group, an ethoxy group, an n-propoxy group and an isopropoxy group.

Examples of the saturated hydrocarbon group substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms include a benzyl group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a toluylmethyl group, a tolylethyl group, a toluylpropyl group, a toluylbutyl group, A methyl group, a methoxyphenylethyl group, a methoxyphenylpropyl group, and a methoxyphenylbutyl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the saturated hydrocarbon group substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a perfluoroethyl group, and a chlorobutyl group.

As R ³ and R ^4, an unsubstituted monovalent saturated hydrocarbon group of 1 to 10 carbon atoms is preferable, a monovalent saturated hydrocarbon group of 1 to 4 carbon atoms is more preferable, and a monovalent saturated hydrocarbon group of 1 to 3 carbon atoms is more preferable.

Examples of the alkyl group having 1 to 6 carbon atoms for R ⁶ and R ⁷ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, Isopentyl group, neopentyl group and the like.

Examples of the aralkyl group having 7 to 10 carbon atoms for R ¹¹ include a benzyl group, a phenylethyl group, and a phenylbutyl group.

Z ⁺ is ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ¹¹ ) ₄ .

As the ⁺ N (R ¹¹ ) _4, it is preferable that at least two of the four R ^{11 s} are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total number of carbon atoms of the four R < ¹¹ > s is preferably from 20 to 80, more preferably from 20 to 60. [

The phenyl group representing R ¹ and R ² may have a substituent. Examples of the substituent halogen ^{atoms, -R 8, -OH, -OR 8} , -SO 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 R 8, -SR 8, -SO 2 R 8, -SO ₃ R ⁸ and -SO ₂ NR ⁹ R ¹⁰ . Among these substituents, -R ⁸ is preferable, and a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is more preferable. In this case, -SO ₃ ^- Z ⁺ is preferably -SO ₃ ^{- +} N (R ¹¹ ) ₄ .

Examples of the phenyl group having a substituent include a toluyl group, a dimethylphenyl group, an ethylphenyl group, a propylphenyl group, an isopropylphenyl group, a methylsulfanylphenyl group and a methylsulfonylphenyl group. Among them, a phenyl group having a substituent at the ortho position with respect to the number of bonds with nitrogen (hand) is preferable.

Preferably, R ¹ and R ² are each independently a phenyl group having a monovalent saturated hydrocarbon group of 1 to 4 carbon atoms, more preferably a toluyl group or a dimethylphenyl group, and an o-toluyl group or a 2,6-dimethylphenyl group More preferable.

R ¹ and R ³ together with the nitrogen atom may form a ring containing a nitrogen atom. That is, a carbon atom on the benzene ring constituting a phenyl group which may have a substituent in R ¹ and an atom constituting a monovalent saturated hydrocarbon group in R ³ are bonded to form a ring containing a nitrogen atom together with a nitrogen atom . R ² and R ⁴ together with the nitrogen atom may form a ring containing a nitrogen atom. That is, a carbon atom on the benzene ring constituting a phenyl group which may have a substituent in R ² and an atom constituting a monovalent saturated hydrocarbon group in R ⁴ are bonded to form a ring containing a nitrogen atom together with a nitrogen atom . Examples of the ring to be formed include the following.

R ⁵ -SO ₃ H, -SO ₃ Examples ^- the Z ⁺ and -SO ₂ NR ⁹ R ¹⁰ are preferred.

As R ⁶ and R ⁷ , a hydrogen atom, a methyl group and an ethyl group are preferable, and a hydrogen atom is more preferable.

m is preferably an integer of 0 to 2, more preferably 1 or 2.

The compound (1) is preferably a compound represented by the formula (2).

[In the formula (2), R ²¹ , R ²² , R ²³ and R ²⁴ independently represent an alkyl group having 1 to 4 carbon atoms.

p and q each independently represent an integer of 0 to 5; When p is 2 or more, plural R ^{23 s} may be the same or different, and when q is 2 or more, plural R ^{24 s} may be the same or different.

Examples of the alkyl group having 1 to 4 carbon atoms representing R ²¹ , R ²² , R ²³ and R ²⁴ include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec- .

R ²¹ and R ²² each independently represent a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms. R ²³ and R ²⁴ are preferably methyl groups.

p and q are preferably an integer of 0 to 2, and are preferably 1 or 2.

As the compound (1), a compound represented by the formula (3) is preferable.

[In the formula (3), R ³¹ and R ³² each independently represent an alkyl group having 1 to 4 carbon atoms.

R ³³ , R ³⁴ , R ³⁵ and R ³⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ³¹ to R ³⁶ include the same groups as described above.

R ³¹ and R ³² each independently represent a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms. It is preferable that R ³³ to R ³⁶ are each independently a hydrogen atom or a methyl group.

Examples of the compound (1) include compounds represented by any one of the formulas (1-1) to (1-15). Among them, the compound represented by the formula (1-1), the formula (1-2) or the formula (1-5) to (1-12) is preferable in that the solubility in an organic solvent is excellent.

Examples of the method for producing the compound (1) include a method of reacting the compound represented by the formula (1a) with the compound represented by the formula (1b) and the compound represented by the formula (1c) in the presence or absence of an organic solvent . It is preferable to react in the absence of solvent in terms of yield. The reaction temperature is preferably 30 ° C to 180 ° C, more preferably 80 ° C to 130 ° C. The reaction time is preferably 1 hour to 12 hours, more preferably 3 hours to 8 hours.

[In formulas (1b) and (1c), R ¹ to R ⁴ each have the same meaning as defined above.]

Examples of the organic solvent include hydrocarbon solvents such as toluene and xylene; Halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and chloroform; Alcohol solvents such as methanol, ethanol and butanol; A nitrohydrocarbon solvent such as nitrobenzene; Ketone solvents such as methyl isobutyl ketone; And amide solvents such as 1-methyl-2-pyrrolidone.

The amount of the compound represented by formula (1b) and the compound represented by formula (1c) is preferably 1 mole or more and 8 mole or less, more preferably 1 mole or less per mole of the compound represented by formula (1a) Or more and 5 moles or less. May be reacted stepwise or simultaneously.

It is preferable that the compound represented by formula (1b) and the compound represented by formula (1c) have the same structure in that the preparation of compound (1) is easy.

The method for obtaining the desired compound (1) from the reaction mixture is not particularly limited and various known methods may be employed. For example, the reaction mixture may be mixed with an acid (e.g., acetic acid or the like), and the precipitated crystals may be collected by filtration. It is preferable that the acid is prepared by preparing an aqueous solution of an acid in advance and then adding the reaction mixture to the aqueous solution. The temperature at the time of adding the reaction mixture is preferably from 10 캜 to 50 캜. Thereafter, stirring is preferably performed at the same temperature for about 0.5 to 2 hours. The crystals obtained by filtration are preferably washed with water or the like, and then dried. If necessary, it may be further purified by a known method such as recrystallization.

The content of the compound (1) in the colored curable resin composition of the present invention is preferably 0.025 mass% or more and 48 mass% or less, more preferably 0.08 mass% or more and 42 mass% Or more and 30 mass% or less. Here, the "total amount of solid content" in the present specification refers to a limited amount of the solvent in the total amount of the colored curable resin composition. The total amount of the solid content and the content of each component relative to the total amount can be measured by a known analytical means such as liquid chromatography or gas chromatography.

When the colorant (A) contains the pigment (A1) and / or the dye (A2) together with the compound (1), the content of the compound (1) is preferably not less than 0.5% by mass and not more than 80% Or less, more preferably 1 mass% or more and 70 mass% or less, and still more preferably 1 mass% or more and 50 mass% or less.

≪ Pigment (A1) >

The pigment (A1) is not particularly limited, and known pigments can be used. For example, the pigment is classified into pigments in the color index (The Society of Dyers and Colourists).

As the pigment, for example, C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139 , 147, 148, 150, 153, 154, 166, 173, 194 and 214;

C.I. Orange pigments such as Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 175, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, Red pigment;

C.I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and 80;

C.I. Violet pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38;

C.I. Green pigments such as Pigment Green 7, 36, and 58;

C.I. Brown pigments such as Pigment Brown 23 and 25;

C.I. Pigment black 1, pigment black 7, and the like.

As the pigment, C.I. Pigment Blue 15, 15: 3, 15: 4, 15: 6 and 60, and C.I. Violet color pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38 and the like are preferable, and C.I. Pigment Blue 15: 3, 15: 6, and C.I. Pigment Violet 23 is more preferable, and C.I. Pigment Blue 15: 6 is more preferable. By including the above-mentioned pigments, in particular, when the colored curable resin composition of the present invention is prepared as a blue colored curable resin composition, the transmission spectrum can be easily optimized, and the light resistance and chemical resistance of the color filter can be improved.

The pigment may be subjected to a surface treatment using a rosin treatment, a pigment derivative in which an acidic group or a basic group is introduced, a graft treatment on the surface of a pigment with a polymer compound or the like, an atomization treatment such as a sulfuric acid atomization method or an organic solvent A cleaning treatment with water or the like, a removal treatment with an ion exchange method of ionic impurities, or the like may be performed.

The pigment preferably has a uniform particle size. By containing the pigment dispersant and performing the dispersion treatment, a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic pigment dispersants. These pigment dispersants may be used alone or in combination of two or more. Examples of the pigment dispersant include trade name KP (manufactured by Shin-Etsu Chemical Co., Ltd.), fluorene (manufactured by Kyoeisha Chemical Co., Ltd.), Solspas (manufactured by Zeneca), EFKA Spur (manufactured by Ajinomoto Fine Techno Co., Ltd.), and Disperbyk (manufactured by Vickers).

When a pigment dispersant is used, the amount thereof is preferably 1% by mass or more and 100% by mass or less, and more preferably 5% by mass or more and 50% by mass or less, based on the pigment (A1). When the amount of the pigment dispersant is within the above range, there is a tendency to obtain a more uniformly dispersed pigment dispersion.

When the colorant (A) contains the pigment (A1), the content of the pigment (A1) is preferably 20 mass% or more and 99.5 mass% or less, more preferably 30 mass% or more and 99 mass% or less based on the total amount of the colorant (A) More preferable.

≪ Dye (A2) >

The dye (A2) is not particularly limited as long as it is different from the compound (1), and known dyes can be used. Examples of the dye (A2) include useful dyes, acid dyes, basic dyes, direct dyes, mordant dyes, amine salts of acid dyes Amide derivatives, and the like. Examples of such dyes include compounds classified in the color index (published by The Society of Dyers and Colourists) as dyes (other than pigments and having a color), dyeing notes And the known dyes described. According to the chemical structure, the azo dye, cyanine dye, triphenylmethane dye, xanthene dye, phthalocyanine dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, , Styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes. Of these, organic solvent-soluble dyes are preferred.

Specifically, C.I. 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162; Solvent Yellow 4 (hereinafter abbreviated as CI Solvent Yellow)

C.I. Solvent Red 45, 49, 125, 130, 218;

C.I. Solvent Orange 2, 7, 11, 15, 26, 56;

C.I. Solvent Blue 4, 5, 37, 67, 70, 90;

C.I. Solvent Green 1, 4, 5, 7, 34, 35, etc. C.I. Solvent dyes,

C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 112, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 87, 215, 198, 206, 211, 215, 216, 217, 218, 219, 288, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 276, 268, 270, 274, 277, 280, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;

C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

C.I. Acid Violet 6B, 7, 9, 17, 19, 30, 102;

C.I. Acid Blue 1, 7, 9, 15, 18, 22, 29, 42, 59, 60, 62, 70, 72, 74, 82, 83, 86, 87, 90, 92, 93, 166, 167, 168, 170, 171, 184, 187, 192, 199, 210, 229, 234, 236, 242, 243, 256, 259, 267, 285, 296, 315, 335;

C.I. C.I., such as Acid Green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, Acid dyes,

C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 136, 138, 141;

C.I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

C.I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

C.I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

C.I. Direct Blue 1, 2, 6, 8, 15, 22, 25, 41, 57, 71, 76, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 198, 199, 200, 201, 202, 203, 207, 209, 210, 202, 203, 207, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;

C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, Direct dyes;

C.I. Disperse Yellow 54, C.I. Disperse Dyes;

C.I. Basic red 1, 10;

C.I. Basic Blue 1, 3, 5, 7, 9, 19, 24, 25, 26, 28, 29, 40, 41, 54, 58, 59, 64, 65, 66, 67, 68;

C.I. Basic green 1 and other C.I. basic dyes,

C.I. Reactive Yellow 2, 76, 116;

C.I. Reactive Orange 16;

C.I. C.I. Reactive dyes,

C.I. Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

C.I. 43, 38, 39, 41, 43, 43, 43, 43, 42, 43, , 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;

C.I. Modern orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

C.I. Modern Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;

C.I. 1, 2, 3, 7, 9, 12, 13, 15, 16, 19, 20, 21, 22, 26, 30, 31, 39, 40, 41, 43, 44, 49, 53, 61 , 74, 77, 83, 84;

C.I. CI. 1, 3, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, Modern dyes,

C.I. C.I. Vat dyes and the like.

These dyes can be appropriately selected in accordance with the spectral spectrum of a desired color filter. Among them, a blue dye, a violet dye and a red dye are preferable.

When the colorant (A) contains the dye (A2), the content of the dye (A2) is preferably 0.5% by mass or more and 35% by mass or less, more preferably 1% by mass or more and 30% More preferable.

As the colorant (A), a colorant comprising the compound (1) and the pigment (A1) and a colorant comprising the compound (1), the pigment (A1) and the dye (A2) are preferable.

When the coloring agent (A) is a coloring agent comprising the compound (1) and the pigment (A1), the content thereof is preferably in the range of

Compound (1); 0.5% by mass or more and 80% by mass or less

A pigment (A1); More preferably 20 mass% or more and 99.5 mass% or less,

Compound (1); 1% by mass or more and 50% by mass or less

Pigment (A); More preferably 50 mass% or more and 99 mass% or less.

When the coloring agent (A) is a coloring agent comprising the compound (1), the pigment (A1) and the dye (A2), the content thereof is preferably

Compound (1); 0.5% by mass or more and 79.5% by mass or less

A pigment (A1); 20 mass% or more and 99 mass% or less

A dye (A2); More preferably 0.5 mass% or more and 35 mass% or less,

Compound (1); 1% by mass or more and 50% by mass or less

A pigment (A1); 49% by mass or more and 98% by mass or less

A dye (A2); More preferably 1% by mass or more and 30% by mass or less.

The content of the colorant (A) is preferably from 5 to 60% by mass, more preferably from 8 to 55% by mass, and still more preferably from 10 to 50% by mass, based on the total amount of solids. When the content of the colorant (A) is within the above range, the color density of the color filter is sufficient and the resin (B) or the polymerizable compound (C) can be contained in a required amount in the composition. A sufficient pattern can be formed.

≪ Resin (B) >

The resin (B) is not particularly limited, but is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6].

(A) (hereinafter also referred to as "(a)") selected from the group consisting of a resin [K1] unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, a cyclic ether structure having a carbon number of 2 to 4 (B) (hereinafter also referred to as "(b)") having an ethylenically unsaturated bond;

The monomer (c) copolymerizable with the resin (K2) (a), (b) and (a) (different from (a) and (b) ≪ / RTI >

Resin [K3] Copolymer of (a) and (c);

Resin [K4] Resin (b) is reacted with a copolymer of (a) and (c);

Resin [K5] Resin (a) is reacted with a copolymer of (b) and (c);

Resin [K6] A resin obtained by reacting (a) a copolymer of (b) and (c) with a carboxylic acid anhydride.

(a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m- and p-vinylbenzoic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;

5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept- 5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept- [2.2.1] hept-2-ene, and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride , Unsaturated dicarboxylic acid anhydrides such as dimethyl tetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-eno anhydride;

(Meth) acryloyloxyalkyl (meth) acrylate of a divalent or higher polyvalent carboxylic acid such as mono [2- (meth) acryloyloxyethyl] succinate, mono [2- ] Esters;

and unsaturated acrylic acids containing a hydroxyl group and a carboxyl group in the same molecule such as? - (hydroxymethyl) acrylic acid.

Of these, acrylic acid, methacrylic acid and maleic anhydride are preferable from the viewpoint of copolymerization reactivity and the solubility of the resulting resin in an aqueous alkali solution.

(b) refers to a polymerizable compound having an ethylenic unsaturated bond and a cyclic ether structure having 2 to 4 carbon atoms (e.g., at least one member selected from the group consisting of oxirane rings, oxetane rings, and tetrahydrofuran rings). (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

In the present specification, the term " (meth) acrylic acid " refers to at least one member selected from the group consisting of acrylic acid and methacrylic acid. The expressions such as "(meth) acryloyl" and "(meth) acrylate" have the same meaning.

(b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter referred to as " b2) "), a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter occasionally referred to as" (b3) "), and the like.

(b1-1) having a structure in which a linear or branched unsaturated aliphatic hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-1)"), an unsaturated alicyclic hydrocarbon is epoxidized (Hereinafter sometimes referred to as " (b1-2) ").

(meth) acrylate,? -methyl glycidyl (meth) acrylate,? -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl Vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? -Methyl- Methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5- ) Styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5- , 3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) have.

(b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (such as Celloxide 2000 manufactured by Daicel), 3,4-epoxycyclohexylmethyl (meth) Cyclohexylmethyl (meth) acrylate (for example, Cyclorom M100, manufactured by Daicel), represented by the formula (I) And a compound represented by the formula (II).

[In the formulas (I) and (II), R ⁵¹ and R ⁵² represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxy group.

X ⁵¹ and X ⁵² represent a single bond, -R ⁵³ -, * -R ⁵³ -O-, * -R ⁵³ -S- or * -R ⁵³ -NH-.

And R ⁵³ represents an alkanediyl group having 1 to 6 carbon atoms.

* Represents the number of bonds with O.]

Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl.

Examples of the alkyl group in which the hydrogen atom is substituted with hydroxy include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, 1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group and 4-hydroxybutyl group.

R ⁵¹ and R ⁵² are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, more preferably a hydrogen atom or a methyl group.

Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane- A 6-diyl group and the like.

X ⁵¹ and X ⁵² are preferably a single bond, a methylene group, an ethylene group, * -CH ₂ -O- and * -CH ₂ CH ₂ -O-, more preferably a single bond, * -CH ₂ CH ₂ -O- (* represents the number of bonds with O).

Examples of the compound represented by the formula (I) include compounds represented by any one of the formulas (I-1) to (I-15). (I-1), (I-3), (I-5), ). ≪ / RTI > More preferably, the compound represented by formula (I-1), formula (I-7), formula (I-9) or formula (I-15) can be mentioned.

Examples of the compound represented by the formula (II) include compounds represented by any one of the formulas (II-1) to (II-15). (II-1), II-3, II-5, II-7, II-9 or II- ). ≪ / RTI > The compound represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15) is more preferred.

The compound represented by formula (I) and the compound represented by formula (II) may be used alone. They may be mixed at an arbitrary ratio. In the case of mixing, the mixing ratio thereof is preferably from 5:95 to 95: 5, more preferably from 10:90 to 90:10, and even more preferably from 20:80 to 90:10 in formula (I) ~ 80: 20.

(b2) is more preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group. methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3- (3-methacryloyloxymethyloxetane) Ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3- 3-ethyl-3-acryloyloxyethyl oxetane, and the like.

As the monomer (b3), a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable. Specific examples of the compound (b3) include tetrahydrofurfuryl acrylate (e.g., Viscot V # 150, Osaka Yuki Kagaku Kogyo Co., Ltd.) and tetrahydrofurfuryl methacrylate.

(b) is preferably (b1) in that reliability of heat resistance, chemical resistance, etc. of the obtained color filter can be further improved. Further, (b1-2) is more preferable in that the storage stability of the colored curable resin composition is excellent.

(meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (Meth) acrylate, cyclohexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (Meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (also referred to in the art as "dicyclopentanyl (meth) acrylate" Tricyclodecyl (meth) acrylate "), tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (dicyclopentenyl (meth) acrylate Acrylate "), dicyclopentane (Meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (Meth) acrylates such as naphthyl (meth) acrylate and benzyl (meth) acrylate;

(Meth) acrylic acid esters having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate;

2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept- Ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept- 2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept- Cyclohexyl [2.2.1] hept-2-ene, 5,6-bis 2,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene and the like such as bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept- Cyclo-unsaturated compounds;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N- Dicarbonylimide derivatives such as N-succinimidyl-3-maleimidepropionate and N- (9-acridinyl) maleimide;

But are not limited to, styrene, -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, Vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

Of these, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and bicyclo [2.2.1] hept-2-ene are preferable from the viewpoint of copolymerization reactivity and heat resistance.

In the resin [K1], the proportion of the structural unit derived from each of the resins [K1]

(a); 2 to 60 mol%

(b); Is preferably 40 to 98 mol%

(a); 10 to 50 mol%

(b); And more preferably 50 to 90 mol%.

When the ratio of the structural unit of the resin [K1] is within the above-mentioned range, there is a tendency that storage stability of the colored curable resin composition, developability in forming a colored pattern, and solvent resistance of the color filter are excellent.

Resin [K1] can be synthesized by, for example, the method described in "Experimental Method of Polymer Synthesis" (published by Otsu Takayuki Co., Ltd., first edition, 1st edition, published on March 1, 1972) . ≪ / RTI >

Specifically, for example, a predetermined amount of (a) and (b), a polymerization initiator and a solvent are placed in a reaction vessel to replace the oxygen with nitrogen, for example, to form a deoxidized atmosphere, followed by heating and heating with stirring . On the other hand, the polymerization initiator and the solvent to be used herein are not particularly limited, and those generally used in this field can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile) and the like) and organic peroxides (benzoyl peroxide and the like) As the solvent, any one that dissolves the respective monomers may be used. As the solvent (E) of the colored curable resin composition, there may be mentioned a solvent described later.

On the other hand, the resulting copolymer may be used as it is, or may be a concentrated or diluted solution, or may be used as a replacement (powder) by re-precipitation or the like. In particular, by using a solvent contained in the colored curable resin composition of the present invention as a solvent in the polymerization, the solution after the reaction can be used as it is for preparing the colored curable resin composition of the present invention, thereby simplifying the production process.

In the resin [K2], the proportion of the structural units derived from each other is preferably from 1 to 100,

(a); 2 to 45 mol%

(b); 2 to 95 mol%

(c); , More preferably 1 to 65 mol%

(a); 5 to 40 mol%

(b); 5 to 80 mol%

(c); And more preferably 5 to 60 mol%.

When the ratio of the structural unit of the resin [K2] is within the above-mentioned range, there is a tendency that the storage stability of the colored curing resin composition, developability in forming the pattern, solvent resistance of the obtained pattern, heat resistance and mechanical strength are excellent.

The resin [K2] can be produced, for example, in the same manner as the method described as the method for producing the resin [K1].

In the resin [K3], the ratio of the respective structural units derived from each other is preferably selected from the group consisting of the total structural units constituting the resin [K3]

(a); 2 to 60 mol%

(c); Is preferably 40 to 98 mol%

(a); 10 to 50 mol%

(c); And more preferably 50 to 90 mol%.

The resin [K3] can be produced, for example, in the same manner as the method described as the method for producing the resin [K1].

The resin [K4] is obtained by obtaining a copolymer of (a) and (c) and adding a cyclic ether having 2 to 4 carbon atoms in (b) to a carboxylic acid and / or carboxylic acid anhydride having (a) can do.

First, a copolymer of (a) and (c) is prepared in the same manner as the method described as the method for producing the resin [K1]. In this case, the proportion of the structural units derived from each of them is preferably the same as that in the resin [K3].

Subsequently, a cyclic ether having 2 to 4 carbon atoms contained in (b) is reacted with a part of the carboxylic acid and / or carboxylic acid anhydride derived from (a) in the copolymer.

Subsequent to the preparation of the copolymer of (a) and (c), the atmosphere in the flask is replaced with air in nitrogen, and (b) a reaction catalyst of a carboxylic acid or carboxylic acid anhydride with a cyclic ether Methyl) phenol) and a polymerization inhibitor (e.g., hydroquinone) are placed in a flask and reacted at 60 to 130 DEG C for 1 to 10 hours, for example, to prepare the resin [K4].

(b) is preferably 5 to 80 moles, more preferably 10 to 75 moles, per 100 moles of (a). Within this range, there is a tendency that the balance between the storage stability of the colored curable resin composition, developability in forming the pattern, solvent resistance of the obtained pattern, heat resistance, mechanical strength and sensitivity becomes good. (B1) is more preferable, and (b1-1) is more preferable for the resin (K4) because the reactivity of the cyclic ether is high and unreacted (b)

The amount of the reaction catalyst to be used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor to be used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b) and (c).

The reaction conditions such as the charging method, the reaction temperature and the time can be appropriately adjusted in consideration of the production facility or the amount of heat generated by polymerization. On the other hand, as in the case of the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production facility or the amount of heat generated by polymerization.

Resin [K5] is a first step, and a copolymer of (b) and (c) is obtained in the same manner as the above-mentioned method for producing Resin [K1]. Similarly to the above, the solution after the reaction may be used as it is, or a concentrated or diluted solution may be used, and the copolymer taken out as a solid (powder) by re-precipitation or the like may be used.

the proportion of the structural units derived from (b) and (c) is preferably within the following range with respect to the total number of moles of the total structural units constituting the copolymer.

(b); 5 to 95 mol%

(c); , More preferably 5 to 95 mol%

(b); 10 to 90 mol%

(c); And more preferably 10 to 90 mol%.

Further, by reacting the carboxylic acid or carboxylic acid anhydride of (a) with a cyclic ether derived from (b) in the copolymer of (b) and (c) under the same conditions as in the production of resin [K4] Resin [K5] can be obtained.

The amount of (a) to be reacted with the copolymer is preferably 5 to 80 moles per 100 moles of (b). (B1) is more preferable, and (b1-1) is more preferable for the resin (K5) because the reactivity of the cyclic ether is high and the unreacted (b)

Resin [K6] is a resin obtained by further reacting a resin [K5] with a carboxylic acid anhydride.

A carboxylic acid anhydride is reacted with a hydroxy group generated by the reaction of a cyclic ether with a carboxylic acid or a carboxylic acid anhydride.

Examples of the carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, Tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hydroamic anhydride). The amount of the carboxylic acid anhydride to be used is preferably 0.5 to 1 mole based on 1 mole of the amount of (a).

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) Resin [K1] such as coalescence; (Meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2 .1.0 ^2.6] decyl acrylate / (meth) resins such as acrylic acid / N- cyclohexyl maleimide copolymer, 3-methyl-3- (meth) acryloyloxyethyl-methyl oxetane / (meth) acrylic acid / styrene copolymer [K2]; Resins [K3] such as benzyl (meth) acrylate / (meth) acrylic acid copolymer and styrene / (meth) acrylic acid copolymer; A resin obtained by adding glycidyl (meth) acrylate to a benzyl (meth) acrylate / (meth) acrylic acid copolymer and a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / styrene / (meth) ) Resin, a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer; A resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, a resin obtained by reacting tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) A resin [K5] such as a resin obtained by reacting a (meth) acrylic acid with a copolymer; A resin such as a resin obtained by further reacting a resin obtained by reacting (meth) acrylic acid with a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate and tetrahydrophthalic anhydride, and the like .

Among them, as the resin (B), resin [K1], resin [K2] and resin [K4] are preferable.

The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000. When the molecular weight is within the above range, the hardness of the coating film is improved, the residual film ratio is high, the solubility of the unexposed portion in the developer is good, and the resolution tends to be improved.

The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

The acid value of the resin (B) is preferably 50 to 170 mg-KOH / g, more preferably 60 to 150 mg-KOH / g, and still more preferably 70 to 135 mg-KOH / g. The acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the resin (B), and can be determined by titration using, for example, an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, and still more preferably from 17 to 55% by mass, based on the total solid content. When the content of the resin (B) is within the above range, a colored pattern can be easily formed, and the resolution and residual film ratio of the colored pattern tends to be improved.

≪ Polymerizable compound (C) >

The polymerizable compound (C) is a compound capable of being polymerized by an active radical and / or an acid generated from heat or the polymerization initiator (D), for example, a compound having a polymerizable ethylenic unsaturated bond, Is a (meth) acrylic acid ester compound.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenic unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa Acrylate, tetrapentaerythritol hexa (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hexa (meth) acrylate, (Meth) acrylate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra Glycol-modified dipentaerythritol hexa (meth) acrylate , Caprolactone-modified pentaerythritol tetra (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate.

Among them, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, and more preferably 250 to 1,500 or less.

The content of the polymerizable compound (C) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, and still more preferably from 17 to 55% by mass, based on the total amount of solids. When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of pattern formation and the chemical resistance of the pattern tend to be improved.

≪ Polymerization initiator (D) >

The polymerization initiator (D) generates active radicals, acids, etc. by the action of light or heat, and any known polymerization initiator can be used as long as it is a compound capable of initiating polymerization.

As the polymerization initiator (D), a polymerization initiator containing at least one member selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds and imidazole compounds is preferable, A polymerization initiator comprising an acyloxime compound is more preferable.

The O-acyloxime compound is a compound having a partial structure represented by formula (d1).

Herein, * represents the number of bonds.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy- 2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan- -Acetoxy-l- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl Benzoyl} -9H-carbazol-3-yl] ethan-1-imine, N- acetoxy- 1- [9- ethyl- 6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropan-1-imine, N-benzoyloxy- 1- [9- ethyl-6- (2-methylbenzoyl) -9H- ] -3-cyclopentylpropan-1-one-2-imine. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (manufactured by BASF) and N-1919 (manufactured by ADEKA) may be used.

The alkylphenone compound is a compound having a partial structure represented by formula (d2) or a partial structure represented by formula (d3). Of these partial structures, the benzene ring may have a substituent.

Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan- 2- (4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane-1-one - on. Commercially available products such as Irgacure (registered trademark) 369, 907 and 379 (manufactured by BASF) may be used.

Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2- 1-hydroxy-2-methyl-1- (4-isopropenylphenyl) propane-1-one, ? -diethoxyacetophenone, benzyldimethylketal, and the like.

From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by formula (d2).

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4- Methyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- 2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4,6-trichloromethyl- Bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- - [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like. Commercially available products such as Irgacure 819 (manufactured by BASF) may be used.

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- 4,4 ', 5,5'-tetraphenylbiimidazole (see JPH06-75372-A, JPH06-75373-A and the like), 2,2'-bis (2-chlorophenyl) 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (alkoxyphenyl) (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (Trialkoxyphenyl) imidazole (for example, see JPS48-38403-B, JPS62-174204-A and the like), imidazole compounds in which the phenyl group at the 4,4'5,5'-position is substituted by a carboalkoxy group (See JPH07-10913-A, for example).

Examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert- butylperoxycarbonyl) benzophenone, Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethyl anthraquinone, and campquinone; Butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with the polymerization initiator D1 (particularly amines) to be described later.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, (4-acetoxyphenyl) dimethylsulfonium p-toluenesulfonate, Benzyl (4-acetoxyphenyl) methylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p- toluenesulfonate, Diphenyl iodonium hexafluoroantimonate, and the like; and nitrobenzenesulfonates, benzoin tosylates, and the like.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is in the above range, high sensitivity is obtained and the exposure time tends to be shortened, so that the productivity is improved.

≪ Polymerization initiator (D1) >

The polymerization initiator (D1) is a compound or a sensitizer used for promoting polymerization of a polymerizable compound initiated polymerization by a polymerization initiator. The polymerization initiator (D1) is usually used together with the polymerization initiator (D).

Examples of the polymerization initiator (D1) include an amine compound, an alkoxyanthracene compound, a thioxanthone compound, and a carboxylic acid compound.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, (Diethylamino) benzophenone, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis , 4'-bis (ethylmethylamino) benzophenone, and the like, among which 4,4'-bis (diethylamino) benzophenone is preferable. And commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) may be used.

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10- Anthracene, and 2-ethyl-9,10-dibutoxyanthracene.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Santon et al.

Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, Diphenylacetic acid, dichlorophenylsulfanyl acetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.

When these polymerization initiator (D1) is used, the amount thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C) to be. When the amount of the polymerization initiator (D1) is in this range, it is possible to form the pattern with higher sensitivity, and the productivity of the pattern tends to be improved.

≪ Organometallic Compound (M) >

An organic metal compound (M) is a visible light region of the maximum molar extinction coefficient (ε) of the (with a wavelength of 380 nm nm~780) (below that there is a case called "ε _M ') is smaller than ε _M of compound (1) Organometallic compounds. The organometallic compound is an organometallic complex or a metal salt of an organic acid in which a negative, neutral or positive ligand is coordinated centering on a metal atom or a metal ion. Among them, it is preferable to dissolve in an organic solvent.

? _M of the organometallic compound (M) was determined by diluting 0.1 g of the organometallic compound (M) with 0.250 L of ethyl lactate to prepare a solution, measuring the absorption spectrum of the solution in a visible light spectrophotometer, Lambert-Beer's law.

When two or more compounds (1) are contained in the colored curable resin composition of the present invention, the compound (1) having the smallest epsilon _M is used as a reference.

And ε _M of the organic metal compound (M) is smaller than ε _M of compound (1), preferably 1000 or less, more preferably 500 or less, more preferably 80 or less still more preferably 100 or less, Particularly preferably 60 or less. If? _M is within the above-mentioned range, the brightness of the color filter tends to be high. On the other hand, when the colored curable resin composition containing the two or more kinds of compound (1) of the present invention, ε _M of the organic metal compound (M) is smaller than ε _M of compound (1) having the smallest ε _M. Further, when the colored curable resin composition of the present invention contains two or more kinds of organometallic compounds (M),? _M of the organometallic compound (M) having the largest? _M is smaller than? _M of the compound (1).

Examples of the metal constituting the metal atom or the metal ion of the organometallic compound (M) include a typical metal and a transition metal.

Examples of the typical metals include Group 1 elements (alkali metals), Group 2 elements (alkaline earth metals), Group 12 elements (Zinc Group), Group 13 Elements (Boron Group), Group 14 Elements ), And the atom of the metal element contained in the group 15 element (nitrogen group).

Specifically, examples of the material include beryllium, magnesium, aluminum, calcium, zinc, gallium, rubidium, strontium, cadmium, Atoms such as In, Sn, Cs, Ba, Hg, Tl, Pb, Bi, .

Among them, a metal such as magnesium (Mg), aluminum (Al), calcium (Ca), zinc (Zn), gallium (Ga), rubidium (Rb), strontium (Sr), indium (In), cesium ) Is more preferable and the valence of aluminum (Al), zinc (Zn), indium (In) and barium (Ba) is more preferable and the atom of aluminum (Al), zinc (Zn) and indium (In) is more preferable.

Examples of the transition metal include Group 3 elements (scandium), Group 4 elements (titanium group), Group 5 elements (vanadium group), Group 6 elements (chromium group), Group 7 elements (manganese group) , The fourth periodic group 8-10 element (iron family), and the fifth periodic group 6 periodic group 8-10 element (platinum group).

Concretely, it is possible to use scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni) Y, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, lanthanum, Ce, Pr, Ge, Pm, Sm, Eu, Gd, Terbium, Dy, Hol, Erbium, (Ir), thulium (Tm), ytterbium (Yb), lutetium (Lu), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium Pt), and gold (Au).

Among them, the first metal such as scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni) (I.e., the fourth period), and cobalt (Co) and nickel (Ni) are more preferable.

The ligand in the case where the organometallic compound (M) is an organometallic complex is not particularly limited and may be a monodentate ligand or a multi-ligand ligand. The molecular weight of one ligand is preferably 20 or more and 500 or less.

Examples of the ligand include tetrahydrofuran, ethylene glycol dimethyl ether, acetonitrile, benzonitrile, oxalate, acetateto, ethanolate, 1-butanethiolate, thiophenolate, 2,2'- Octyl) phenolate, 2,4-pentanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, trifluoro-2,4-pentanedione, hexafluoro- N, N ', N < / RTI > (N, N'-diphenylmethylaniline, '-Tetramethylethylenediamine, 1,2-diaminocyclohexane, 2,2'-bipyridine, 1,10-phenanthroline, ethylenediamine tetraacetate, 1,4,8,11-tetraazacyclo Tetradecane, tris (2-aminoethyl) amine, triethylphosphine, tributylphosphine, tricyclohexylphosphine, dimethylphenylphosphine, triphenylphosphine, Cyclopentadiene, cyclopentadiene, cyclooctene, 1,5-cyclooctadiene, bicyclo [2.2.1] hept-2,5-diene, benzene, naphthalene, Allyl, and the like.

Preferable examples of the ligand are those which do not contain an aromatic ring in the ligand and include acetates, acetyl acetonates, hexafluoroacetyl acetonates, diethyl dithiocarbamates and di-n-butyl dithiols More preferred is an oxcarbamate.

The organometallic complex may have at least one ligand derived from the organic compound as long as it has at least one ligand. Examples of such ligands include fluoro, chloro, bromo, iodo, hydroxy, aqua, oxo, peroxo, carbonyl, carbonato, cyano, amine, sulfato, nitro, nitrito, phosphato, Thiocyanato, isothiocyanato, and the like.

When the organometallic compound (M) is a metal salt of an organic acid, the molecular weight of one organic acid is preferably 20 or more and 500 or less.

Examples of the organic acid include dimethyldithiocarbamic acid, diethyldithiocarbamic acid, dibutyldithiocarbamic acid, N, N-bis (2-hydroxyethyl) dithiocarbamic acid, N- N, N-dibenzyldithiocarbamic acid, diethyldithiophosphoric acid, diisopropyldithiophosphoric acid, 2-hydroxypropanoic acid, stearic acid, tartaric acid, and oxalic acid.

Examples of the organometallic compound (M) include aluminum tris (2-hydroxypropanoate), bis (2-ethylhexanoate) hydroxy aluminum, bis (2-sulfanylpyridine-N-oxide) zinc, bis (Barium stearate), barium tartarate, barium oxalate, compounds described in JP2011-118365-A and JP2004-295116-A, and the like can be mentioned .

Among them, an organometallic compound containing at least one group selected from the group consisting of -C (= O) - and -C (= S) - is preferable, and a compound represented by the formula (F1) F2), and hydrates thereof. The compound represented by Formula (I) is more preferably at least one compound selected from the group consisting of compounds represented by Formula If the organometallic compound (M) is a compound of these, the solubility in an organic solvent tends to be improved.

[In the formula (F1), W ¹ , W ² , M ¹ and x each have the same meaning as defined above.]

[In formula ^{(F2), W 3, W} 4, M 2 , and y represents the same meanings, respectively.]

Examples of the monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms in W ¹ and W ² include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, . Examples of the monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms in which the hydrogen atom is substituted with a hydroxy group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1- -Hydroxypropyl group, 1-hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, Butyl group and the like. Among them, preferred are an ethyl group, a butyl group and a 2-hydroxyethyl group.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in W ¹ and W ² include an aryl group such as a phenyl group, a toluyl group, a xylyl group, a propylphenyl group and a butylphenyl group; And an aralkyl group such as a benzyl group. Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in which the hydrogen atom is substituted by a hydroxy group include a hydroxyphenyl group and a hydroxymethylphenyl group. Among them, phenyl group and benzyl group are preferable.

Examples of the monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms in W ³ and W ⁴ include the same groups as those in W ¹ and W ² .

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom.

Examples of the monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms in which the hydrogen atom is substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a trifluoroethyl group, a chloromethyl group, a chloroethyl group, a dichloroethyl group, , A chlorobutyl group, a bromobutyl group, and an iodobutyl group. Among them, a methyl group, a tert-butyl group or a trifluoromethyl group is preferable.

Examples of the compound represented by the formula (F1) include bis [N, N-bis (2-hydroxyethyl) dithiocarbamate] zinc, bis (N, N-dimethyldithiocarbamate) Bis (N, N-dibutyldithiocarbamate) zinc, bis (N-ethyl-N-phenyldithiocarbamate) Dibenzyldithiocarbamic acid) zinc, and the like.

Examples of the compound represented by the formula (F2) include tris (2,4-pentanedione) aluminum (III), tris (trifluoro-2,4-pentanedionato) aluminum (III) Pentanedionato) indium (III), tris (2,2,6,6-tetramethyl-3,5-heptanedionato) indium (III), tris (trifluoro-2,4-pentanedionato) indium (III), barium (2,4-pentanedione) barium, bis (hexafluoro-2,4-pentanedione) barium, bis (2,2,6,6-tetramethyl- Bis (2,4-pentanedione) nickel (II), bis (N, N-dibutyldithiocarbamate) nickel (II) (II), bis (hexafluoro-2,4-pentanediono) cobalt (II), and the like.

Examples of the organometallic compound (M) include bis (2,4-pentanedione) nickel (II), bis (2,4-pentanediono) cobalt (II), tris ), Tris (2,4-pentanedionato) aluminum (III), bis (hexafluoro-2,4-pentanediono) cobalt (II), bis (N, N-dibutyldithiocarbamate) Zinc, bis [N, N-bis (2-hydroxyethyl) dithiocarbamate] zinc and hydrates thereof are preferable. These compounds are preferable because a color filter of high contrast can be obtained, and the solubility of the compound in an organic solvent tends to be high, so that a color filter having less foreign matter can be obtained.

The content of the organometallic compound (M) is preferably 0.1 part by mass or more and 20 parts by mass or less, more preferably 0.5 part by mass or more and 15 parts by mass or less, based on 100 parts by mass of the total amount of the resin (B) And more preferably 1 part by mass or more and 10 parts by mass or less. When the content of the organic metal compound (M) is within the above range, a color filter having higher brightness and contrast can be obtained.

≪ Solvent (E) >

The solvent (E) is not particularly limited, and a solvent commonly used in this field can be used. For example, an ester solvent (a solvent containing -COO- in the molecule and not containing -O-), an ether solvent (a solvent containing -O- and no -COO- in the molecule), an ether ester solvent ( A solvent containing -COO- and -O- in a molecule), a ketone solvent (a solvent containing -CO- in the molecule and not including -COO-), an alcohol solvent (containing OH in the molecule, -O- , -CO- and -COO-), an aromatic hydrocarbon solvent, an amide solvent, dimethylsulfoxide, and the like.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, Butyl, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1 , 4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, .

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, Methoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, Methyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, propyleneglycol monomethyl ether acetate, Ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol moiety N-butyl ether acetate and the like.

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4- Cyclohexanone, isophorone, and the like.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin and the like.

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.

Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.

Among these solvents, an organic solvent having a boiling point of 120 占 폚 or more and 180 占 폚 or less at 1 atm is preferable from the viewpoint of coatability and drying property. Examples of the solvent (E) include propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4- Hydroxy-4-methyl-2-pentanone and N, N-dimethylformamide are preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate and ethyl 3-ethoxypropionate are more preferable.

The content of the solvent (E) is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass, based on the total amount of the colored curable resin composition. In other words, the solid content of the colored curable resin composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass.

When the content of the solvent (E) is within the above range, the flatness at the time of coating becomes better, and there is no fear of lack of color density when the color filter is formed, and the display characteristics tend to be good.

≪ Surfactant (F) >

Examples of the surfactant (F) include a silicone surfactant, a fluorinated surfactant, and a silicon surfactant having a fluorine atom. These may have a polymerizable group in the side chain.

Examples of the silicone surfactant include a surfactant having a siloxane bond in the molecule. Concretely, it is preferable to use a silicone resin such as diolefin silicone DC3PA, copper SH7PA, copper DC11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH8400 (trade name, manufactured by Dow Corning Co., Ltd.), KP321, KP322, KP323, KP326, KP340 and KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan Joint- .

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule. Concretely, it is possible to use a flour (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megapark (registered trademark) F142D, copper F171, copper F172, copper F173, copper F177 copper copper F554 copper (Registered trademark) EF301, EF303, EF351, EF352 (manufactured by MISS) and Saffron (manufactured by Mitsubishi Materials Corporation), RS-718-K S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemicals Co., Ltd.).

Examples of the silicone surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples thereof include Megapark (registered trademark) R08, BL20, F475, F477 and F443 (manufactured by DIC).

These surfactants may be used singly or in combination of two or more kinds.

The content of the surfactant (F) is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass or less, further preferably 0.01% by mass or more relative to the total amount of the colored curable resin composition 0.05% by mass or less. On the other hand, the content of the pigment dispersant is not included in this content. When the content of the surfactant (F) is within the above range, the flatness of the coating film can be improved.

≪ Other components >

The colored curable resin composition of the present invention may contain additives known in the art such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents and the like, if necessary.

≪ Process for producing colored curable resin composition >

The colored curable resin composition of the present invention can be obtained, for example, by mixing the compound (1), the resin (B), the polymerizable compound (C), the polymerization initiator (D) and the organometallic compound (M) (A2), a polymerization initiator (D1), a surfactant (F), a solvent (E) and other components.

When the pigment (A1) is contained, it is preferable to mix the pigment (A1) with a part or the whole of the solvent (E) in advance and disperse by using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 탆 or less Do. At this time, if necessary, a part or all of the resin (B) and the pigment dispersant may be blended. The desired colored curable resin composition can be prepared by mixing the remaining components or the like to the obtained pigment dispersion to a predetermined concentration.

The dye (A2) in the case of containing the compound (1) and the dye (A2) may be previously dissolved in a part or all of the solvent (E) to prepare a solution in advance. The solution is preferably filtered through a filter having a pore diameter of about 0.01 to 1 mu m.

The colored curable resin composition after mixing is preferably filtered with a filter having a pore diameter of about 0.01 to 10 mu m.

≪ Color filter and manufacturing method of liquid crystal display device >

Examples of a method for producing a coloring pattern of a color filter from the colored curable resin composition of the present invention include a photolithographic method, an inkjet method, and a printing method. Among them, the photolithographic method is preferable. In the photolithography method, the colored curable resin composition of the present invention is applied to a substrate, and a volatile component such as a solvent is removed and dried to form a composition layer. Then, the composition layer is exposed through a photomask to perform development. After development, a colored pattern can be formed by heating as required. In the method for forming a colored pattern, a colored coating film which is a cured product of the composition layer can be formed by not using and / or not developing a photomask when exposed. The coloring pattern and the colored coating film thus obtained can be used as a color filter.

The film thickness of the color filter to be produced is not particularly limited and may be suitably adjusted in accordance with the purpose and application, and is, for example, from 0.1 to 30 탆, preferably from 0.1 to 20 탆, more preferably from 0.5 to 6 탆.

Examples of the substrate include glass plates such as quartz glass, borosilicate glass, alumina silicate glass and soda lime glass whose surface is coated with silica, resin plates such as polycarbonate, polymethylmethacrylate, and polyethylene terephthalate, silicon, A silver / copper / palladium alloy thin film, or the like is formed. A separate color filter layer, a resin layer, a transistor, a circuit, and the like may be formed on these substrates.

Next, a method of forming a pattern on a glass substrate on which a thin film transistor (hereinafter referred to as " TFT ") is formed will be described.

Specifically, a plurality of TFTs 22 are formed for each pixel on a glass substrate 21 by a known method such as a photolithography technique (see FIG. 1). The TFT 22 includes a gate electrode 22a formed of, for example, molybdenum (Mo) on the glass substrate 21 and constituting a part of a gate line, a nitride film (SiN _x ) formed on the gate electrode 22a, deposition of the oxide film (SiO ₂₎ gate insulating film (22b) and a polycrystalline silicon film (22c) with, for example, an oxide film (SiO ₂₎ and a nitride film (SiN _x) formed on the gate insulating film (22b) formed of a stacked film of the And a protective film 22d formed by a film. A region opposite to the gate electrode 22a of the polycrystalline silicon film 22c is a channel region of the TFT 22 and both sides of the channel region serve as a source region or a drain region. The source region of the polycrystalline silicon film 22c is electrically connected to the signal line 27 formed of, for example, aluminum (Al) through a connection hole (contact hole) formed in the protective film 22d. On the other hand, the drain region of the polysilicon film 22c is electrically connected to the pixel electrode 24 through a connection hole (contact hole) 201 as described later.

Alignment marks (not shown) are formed on the glass substrate 21 simultaneously with the TFTs 22 when a plurality of TFTs 22 are formed on the glass substrate 21 for each pixel. This alignment mark serves as a reference for positioning in the color filter layer 23 forming process as will be described later. On the other hand, these alignment marks can also be used as a mark serving as a reference for bonding the drive substrate and the counter substrate. The alignment mark can be formed in the same step using at least one layer in forming a metal layer such as wiring or a polycrystalline silicon layer in the manufacturing process of the TFT 22. [

Subsequently, the colored curable resin composition of the present invention is applied onto the TFT 22 and the glass substrate 21 on which the alignment mark is formed, and the volatile components such as a solvent are removed by heating and drying (prebaking) and / And dried to form a composition layer having a film thickness of 0.5 to 5.0 mu m, for example, 1.0 mu m.

Examples of the application method include a spin coat method, a slit coat method, and a slit & spin coat method.

The temperature in the case of heat drying is preferably 30 to 120 占 폚, more preferably 50 to 110 占 폚. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.

In the case of carrying out the reduced pressure drying, it is preferably carried out at a temperature of 20 to 25 캜 under a pressure of 50 to 150 Pa.

Subsequently, ultraviolet rays are irradiated to the composition layer through a photomask (not shown), and unnecessary portions (unexposed portions) are selectively removed by a developer to form connection holes (not shown) reaching the drain regions of the polysilicon film 22c The contact hole) 201 is formed, the pixel electrode is washed with water.

By the development, the unexposed portion of the composition layer is dissolved and removed in the developer. As the developer, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, tetramethylammonium hydroxide or the like is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10 mass%, and more preferably 0.03 to 5 mass%. In addition, the developer may contain a surfactant.

The developing method may be any of a puddle method, a dipping method and a spraying method. Further, the substrate may be inclined at an arbitrary angle at the time of development.

Thereafter, in order to reflow and / or cure the composition layer in which the connection hole (contact hole) 201 is formed, it is preferable to heat the composition layer at a temperature in the range of 150 to 250 占 폚, preferably 160 to 235 占 폚, 120 minutes is preferable, and heating is performed for 10 to 60 minutes. Thus, the colored curable resin composition layer 23A is formed. This colored curable resin composition layer 23A corresponds to the color filter of the present invention.

This operation is repeated to form the colored curable resin composition layer 23A from the red colored curable resin composition, the green colored curable resin composition and the blue colored curable resin composition, respectively, so that the red filter 23a, A color filter layer 23 including a blue filter 23b and a blue filter 23c is formed (see Fig. 2). The region between the filters of the color filter layer 23 is a mixed region of adjacent colors. This region is a light shielding region opposed to the signal line 27, so there is no particular problem in terms of quality. On the other hand, the area between the filters may not be colored.

Next, for example, a photosensitive resin film 29 as a protective film having a thickness of 0.3 to 2.0 mu m is formed, for example, so as to cover the color filter layer 23 by a spin coating method. Subsequently, the photosensitive resin film 29 is irradiated with ultraviolet rays through a photomask (not shown), and a region corresponding to the connection hole 201 and unnecessary portions are selectively removed by a developing solution to form the polycrystalline silicon film 22c. (Contact hole) 202 reaching the drain region of the semiconductor substrate 201, and then washed with water. Thereafter, for reflow (reflow) of the photosensitive resin film 29, it is heated at a temperature ranging from 100 to 300 캜, for example, 200 캜. Then, in order to remove residues such as dyes and organic matter deposited in the contact holes 202, etching is performed by oxygen plasma, and etching is performed by, for example, dilute hydrofluoric acid to remove the oxide film formed by the oxygen plasma.

Then, a transparent conductive material such as ITO (Indium-Tin Oxide: an oxide mixture film of indium and tin) is formed on the photosensitive resin film 29 by, for example, sputtering. The ITO film is patterned by photolithography and etching Thereby forming a transparent pixel electrode 24 (see Fig. 3). On the other hand, the pixel electrode 24 may be formed of a metal such as aluminum (Al) or silver (Ag), depending on the device to be manufactured. Thereafter, an alignment film is formed by a known method, and then the liquid crystal display device can be manufactured by joining the driving substrate and the counter substrate.

According to the colored curable resin composition of the present invention, a color filter having excellent brightness and contrast can be produced. This color filter is useful as a color filter used in a display device (e.g., a liquid crystal display device, an organic EL device, an electronic paper, etc.) and a solid-state image pickup device.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. In the examples, "%" and "parts" indicating the content or amount are based on mass unless otherwise specified.

In the following synthesis examples, the compound was identified by mass analysis (LC: Agilent 1200 type, MASS; manufactured by Agilent, LC / MSD type).

[Synthesis Example 1]

A solution obtained by mixing 20 parts of the compound represented by the formula (1a) and 200 parts of N-ethyl-o-toluidine (Wako Pure Chemical Industries, Ltd.) under light-shielding conditions was stirred at 110 ° C for 6 hours. The obtained reaction solution was cooled to room temperature, added to a mixed solution of 800 parts of water and 50 parts of 35% hydrochloric acid, and the mixture was stirred at room temperature for 1 hour to precipitate crystals. The precipitated crystals were collected as a residue of suction filtration and dried to obtain 24 parts of a compound represented by the formula (1-1). The yield was 80%.

Identification of the compound represented by the formula (1-1)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 603.4

Exact Mass: 602.2

[Synthesis Example 2]

(1-6) was obtained in the same manner as in Synthesis Example 1 except that N-isopropyl-2,6-dimethylaniline was used instead of N-ethyl-o-toluidine.

Identification of the compound represented by the formula (1-6)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 659.4

Exact Mass: 658.3

[Synthesis Example 3]

A mixture of a compound represented by the formula (A2-1a) and a compound represented by the formula (A2-1b) (trade name: Chugai Aminol Fast Pink R; manufactured by Juga Igasai) was added to a flask equipped with a condenser and a cooling tube , 150 parts of chloroform and 8.9 parts of N, N-dimethylformamide were charged and 10.9 parts of thionyl chloride was added dropwise while maintaining the temperature at 20 占 폚 or lower with stirring. After completion of the dropwise addition, the temperature was raised to 50 캜, and the reaction was maintained at the same temperature for 5 hours and then cooled to 20 캜. After cooling, the reaction solution was added dropwise with stirring a mixture of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine while keeping the temperature at 20 ° C or lower. Thereafter, the reaction was carried out by stirring at the same temperature for 5 hours. Subsequently, the obtained reaction mixture was distilled off with a rotary evaporator, and then a small amount of methanol was added thereto. This mixture was added to a mixed solution of 375 parts of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water and dried under reduced pressure at 60 ° C to obtain a dye (A2-1) (a compound represented by the formula (A2-1-1) to (A2-1-8) ) Was obtained.

[Synthesis Example 4]

Nitrogen was flowed at 0.02 L / min in a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, and 305 parts of ethyl lactate was added and heated to 70 캜 with stirring. Subsequently, 60 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate (the compound represented by the formula (I-1) and the compound represented by the formula (II-1) : 50) and 140 parts of ethyl lactate to prepare a solution, and this solution was dropped into a flask kept at 70 캜 for 4 hours by using a dropping funnel.

On the other hand, a solution prepared by dissolving 30 parts of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 225 parts of ethyl lactate was added dropwise to the flask over 4 hours using a separate dropping funnel. After the dropwise addition of the polymerization initiator solution was completed, the solution was maintained at 70 캜 for 4 hours and then cooled to room temperature to obtain a polymer having a weight average molecular weight (Mw) of 1.3 x 10 ⁴ , a molecular weight distribution of 2.5, a solid content of 35.4% A resin B1 solution having an acid value of 103 mgKOH / g was obtained. Resin B1 has the following structural unit.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in Synthesis Example were measured by the GPC method under the following conditions.

Device; K2479 (manufactured by Shimadzu Seisakusho Co., Ltd.)

column; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ℃

menstruum; THF (tetrahydrofuran)

Flow rate; 1.0 mL / min

Detector; RI

Calibration standards; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by TOSOH CORPORATION)

The ratio (Mw / Mn) of the weight average molecular weight and the number average molecular weight in terms of polystyrene obtained in the above was regarded as molecular weight distribution.

Examples 1 to 6 and Comparative Example 1

Each component was mixed so as to have the composition shown in Table 1 to obtain a colored curable resin composition.

¹⁾ " A1-1 " was preliminarily dispersed by mixing with an acrylic pigment dispersant and an amount of propylene glycol monomethyl ether acetate as described in " E- ^{13) &} quot ;.

²⁾ "E-1 ²⁾ " represents the sum of propylene glycol monomethyl ether acetate content.

Each component in Table 1 shows the following.

(A) Colorant: 1-1: Compound represented by formula (1-1)

(A) Colorant: 1-6: Compound represented by formula (1-6)

(A) Colorant: A1-1: C.I. Pigment Blue 15: 6 (pigment)

(A) Colorant: A2-1: Dye (A2-1)

(B) Resin: B-1: Resin B1 solution

(C) Polymerizable compound: dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.)

(D) A polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE 01,

(M) Organometallic compound: M-1: Bis (dibutyldithiocarbamic acid) zinc

(M) Organometallic compound: M-2: Bis [bis (2-hydroxyethyl) dithiocarbamic acid] Zinc

(M) Organometallic compound: M-3: tris (2,4-pentanedione) indium

(M) Organometallic compound: M-4: Tris (2,4-pentanedione) aluminum

(M) Organometallic compound: M-5: Bis (2,4-pentanedione) nickel (II)

(M) Organometallic compound: M-6: Bis (2,4-pentanedionato) cobalt (II)

(E) Solvent: E-1: Propylene glycol monomethyl ether acetate

(E) Solvent: E-2: Propylene glycol monomethyl ether

(E) Solvent: E-3: Ethyl lactate

(F) Surfactant: fluorine surfactant (Megapark (registered trademark) F554, manufactured by DIC Corporation)

[Calculation of molar extinction coefficient]

Each sample was weighed in a measuring flask of 0.1 g, and then diluted to 0.250 L with ethyl lactate. The absorption spectrum of this solution was measured with a spectrophotometer (V-650DS; manufactured by Nihon Bunko Co., Ltd.) (quartz cell, optical path length: 1 cm), and the absorption spectrum was measured using a Lambert- The maximum value [? _M ] of the molar extinction coefficient? The results are shown in Table 2.

sample Maximum value of molar extinction coefficient
[(L / (mol · cm)] The compound represented by the formula (1-1) 10360 The compound represented by the formula (1-6) 10199 The dye (A2-1) 8031 Bis (dibutyldithiocarbamic acid) zinc 55 Bis [bis (2-hydroxyethyl) dithiocarbamic acid] zinc 49 Tris (2,4-pentanedionato) indium (III) 35 Tris (2,4-pentanedione) aluminum (III) 35 Bis (2,4-pentanedione) nickel (II) 30 Bis (2,4-pentanedione) cobalt (II) 38

[Formation of coloring pattern]

The colored curable composition was applied on a 2 inch square glass substrate (Eagle XG; Corning) by spin coating, and then prebaked at 100 ° C for 3 minutes to obtain a colored composition layer. After cooling, the glass substrate with the coloring composition layer formed thereon and the photomask made of quartz glass were set to 100 mu m in an interval of 150 mJ / cm < 2 > (manufactured by Toshiba Corporation) And irradiated with light at an exposure amount (based on 365 nm). As the photomask, a substrate having a 100 占 퐉 line and space pattern was used. After the light irradiation, the coating film was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 DEG C for 80 seconds, washed with water, and postbaked in an oven at 220 DEG C for 20 minutes , And a coloring pattern was obtained.

[Measurement of film thickness]

The film thickness of the resulting colored pattern was measured using a film thickness measuring device (DEKTAK3, manufactured by Nihon Shinkuigi Co., Ltd.)). The results are shown in Table 3.

[Evaluation of color]

Spectroscopy was performed using a colorimeter (OSP-SP-200, manufactured by Olympus Corporation) with respect to the obtained color pattern on the glass substrate, and the xy chromaticity coordinates (x , y) and the tristimulus value Y were measured. The larger the value of Y, the higher the brightness. The results are shown in Table 3.

[Evaluation of contrast]

Except that exposure was performed without using a photomask, a colored coating film was formed on the glass substrate by the same operation as formation of a colored pattern. Using a contrast colorimeter (CT-1; manufactured by Tsubosaka Denshoku Co., Ltd., detector: BM-5A, light source: F-10), the obtained coating film was subjected to contrast measurement with a blank value of 30,000. A glass substrate on which a colored coating film was formed was sandwiched by a polarizing film (POLAX-38S, manufactured by LuKeo Corporation) to obtain a measurement sample. The results are shown in Table 3.

From the results of the examples, it was confirmed that the coloring pattern obtained from the colored curable resin composition of the present invention exhibited a high brightness of blue and a high contrast. From this, it can be seen that the pattern obtained from the colored curable resin composition of the present invention is useful as a high-definition color filter, and the display device including the color filter has excellent display characteristics.

According to the colored curable resin composition of the present invention, a high-definition color filter can be formed.

21: glass substrate 22: TFT (switching element)
22a: gate electrode 22b: gate insulating film
22c: polycrystalline silicon film 22d: protective film
23: color filter layer 23A: colored curable resin composition layer (color filter)
23a: Red filter 23b: Green filter
23c: blue filter 24: pixel electrode
27: Signal line 29: Photosensitive resin film (protective film)
201, 202: Connection holes

Claims (5)

A colored curable resin composition comprising a colorant, a resin, a polymerizable compound, a polymerization initiator, and an organometallic compound,
Wherein the colorant is a colorant comprising a compound represented by the following formula (1)
Wherein the organometallic compound is at least one selected from the group consisting of a compound represented by the following formula (F1), a compound represented by the following formula (F2), and a hydrate thereof,
Wherein the maximum value of the molar extinction coefficient in the visible light region of the organic metal compound is smaller than the maximum value of the molar extinction coefficient in the visible light region of the compound represented by the formula (1).

[In the formula (1), R ¹ and R ² each independently represent a phenyl group which may have a substituent.
R ³ and R ⁴ each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom, and the aromatic hydrocarbon The hydrogen atom contained in the group may be substituted with an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and -CH ₂ - included in the saturated hydrocarbon group may be replaced by -O-, -CO- or -NR ¹¹ - And may be substituted.
R ¹ and R ³ may form a ring including a nitrogen atom together with a nitrogen atom, and R ² and R ⁴ may form a ring including a nitrogen atom together with a nitrogen atom.
R ⁵ is _{-OH, -SO 3 H, -SO 3} - of _{^{Z +, -CO 2 R 8,}} -SO 3 R 8 or _{^{-SO 2 NR 9 R 10 - Z}} +, -CO 2 H, -CO 2 .
R ⁶ and R ⁷ independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents an integer of 0 to 4; When m is 2 or more, plural R ^{5 s} may be the same or different.
R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
Z ⁺ represents ⁺ N (R < ¹¹ >) ₄ , Na ⁺ or K ⁺ .
R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and R ⁹ and R ¹⁰ may be bonded to each other to form a 3- to 10-membered nitrogen-containing heterocycle together with the nitrogen atom .
R ¹¹ each independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.

In Formula (F1), W ¹ and W ² each independently represent a monovalent aliphatic hydrocarbon group of 1 to 6 carbon atoms or a monovalent aromatic hydrocarbon group of 6 to 10 carbon atoms, and the aliphatic hydrocarbon group and the aliphatic hydrocarbon group contained in the aromatic hydrocarbon group The hydrogen atom may be substituted with a hydroxy group.
M ¹ represents a metal atom.
x represents an integer of 1 to 3, and when x is 2 or more, a plurality of W ¹ and W ² may be the same or different.

[In the formula (F2), W ³ and W ⁴ each independently represent a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, and the hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with a halogen atom.
M ² represents a metal atom.
y represents an integer of 1 to ^3, and when y is 2 or more, a plurality of W ³ and W ⁴ may be the same or different. The colored curable resin composition according to claim 1, wherein the colorant further comprises a pigment. A color filter formed by the colored curable resin composition according to claim 1 or 2. A display device comprising the color filter according to claim 3. delete

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